Color filter composition

ABSTRACT

The invention relates to a color filter composition comprising a) a photoresist binder, b) a transparent pigment, c) optionally a solvent and/or optionally a photoinitiator or a photolatent catalyst, d) a dispersant which is a polymer or copolymer obtainable by a process comprising the steps of a1) polymerizing in a first step one or more ethylenically unsaturated monomers in the presence of at least one nitroxylether having the structural element wherein X represents a group having at least one carbon atom and is such that the free radical X derived from X is capable of initiating polymerization; or a2) polymerizing in a first step one or more ethylenically unsaturated monomers in the presence of at least one stable free nitroxyl radical and a free radical initiator; wherein at least one monomer used in the steps a1) or a2) is a C 1 -C 6  alkyl or hydroxy C 1 -C 6  alkyl ester of acrylic or methacrylic acid; and a second step b) comprising the modification of the polymer or copolymer prepared under a1) or a2) by a transesterification reaction, an amidation, hydrolysis or anhydride modification or a combination thereof, and optionally in addition by quaternization.

The present invention relates to a color filter composition and to amethod for producing a color filter.

Typical methods for producing color filters are, for example, dyeingmethod, printing method, pigment dispersion method and electrodepositionmethod. Among them, particularly, the pigment dispersion method iswidely used owing to the high precision in the position of color filterpixels, film thickness and the like, excellent durability such as lightresistance and thermal resistance, and less defects of pinhole and thelike. In the pigment dispersion method a pigment-dispersedphotosensitive resin layer is formed on a substrate and patterned into asingle-color pattern. This process is repeated three times to obtain R,G, and B color filter layers.

The Japanese Patent Publication JP2002031713 (Mitsubishi) discloses analkaline developable composition for the manufacturing of a colorfilter. The composition for the color filter contains a binder resinand/or a compound having a polymerizable group, provided with an acidicgroup (1), a pigment (2) and a dispersing agent (3). The dispersingagent is an A-B block copolymer consisting of an A block with aquaternary ammonium base in a side chain.

The Japanese Patent Publication JP2004339330 (Dainippon Printing)discloses a method for producing a color filter by using a thermosettingink.

The pigment dispersion for the thermosetting ink and the thermosettingink comprise each at least a pigment, a pigment dispersant composed of acopolymer, which contains a molecular structure in which at least aconstituent unit containing a specific quaternary ammonium base and aconstituent unit containing a specific ester structure are coupled.

There is still a need to find further suitable dispersants havingimproved dispersing properties.

It has now been found that copolymers prepared by a controlled radicalpolymerization process as disclosed in the International PublicationWO2006074969 (Application No. PCT/EP2006/050000 show improved dispersingproperties when used as color filter compositions.

Thus, the invention relates to a color filter composition comprising

-   -   a) a photoresist binder,    -   b) a transparent pigment,    -   c) optionally a solvent and/or optionally a photoinitiator or a        photolatent catalyst,    -   d) a dispersant which is a polymer or copolymer obtainable by a        process comprising the steps of        -   a1) polymerizing in a first step one or more ethylenically            unsaturated monomers in the presence of at least one            nitroxylether having the structural element

-   -   -    wherein X represents a group having at least one carbon            atom and is such that the free radical X• derived from X is            capable of initiating polymerization; or        -   a2) polymerizing in a first step one or more ethylenically            unsaturated monomers in the presence of at least one stable            free nitroxyl radical

-   -   -    and a free radical initiator; wherein at least one monomer            used in the steps a1) or a2) is a C₁-C₆alkyl or hydroxy            C₁-C₆ alkyl ester of acrylic or methacrylic acid; and        -   b) in a second step modification of the polymer or copolymer            prepared under a1) or a2) by a transesterification reaction,            an amidation, hydrolysis or anhydride modification or a            combination thereof; and optionally in addition by            quaternization.

DEFINITIONS

The term photoresist binder refers to a photosensitive resin which ispreferably an acid-curable resin or a photo curable resin such asacrylate, photo curable acrylate oligomer, polyester, alkyd, melamine,urea, epoxy and phenolic resins or mixtures thereof. Acid-curable resinsof that kind are generally known and are described, for example, in“Ullmann's Encyclopdie dertechnischen Chemie”, Edition 4, Vol. 15(1978), pp. 613-628. Preferred are (meth)acrylate/(meth)acrylic acidcopolymers.

Preferable examples of copolymers are copolymers of methyl(meth)acrylate and (meth)-acrylic acid, copolymers of benzyl(meth)acrylate and (meth)acrylic acid, copolymers of methyl(meth)acrylate/, ethyl (meth)acrylate and (meth)acrylic acid, copolymersof benzyl (meth)acrylate, (meth)acrylic acid and styrene, copolymers ofbenzyl (meth)acrylate, (meth)acrylic acid and 2-hydroxyethyl(meth)acrylate, copolymers of methyl (meth)acrylate/, butyl(meth)acrylate, (meth)acrylic acid and styrene, copolymers of methyl(meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid andhydroxyphenyl (meth)acrylate, copolymers of methyl (meth)acrylate,(meth)acrylic acid and polymethyl (meth)acrylate macromonomer,copolymers of benzyl (meth)acrylate, (meth)acrylic acid and polymethyl(meth)acrylate macromonomer, copolymers of tetrahydrofurfuryl(meth)acrylate, styrene and (meth)acrylic acid, copolymers of methyl(meth)acrylate, (meth)acrylic acid and polystyrene macro-monomer,copolymers of benzyl (meth)acrylate, (meth)acrylic acid and polystyrenemacro-monomer, copolymers of benzyl (meth)acrylate, (meth)acrylic acid,2-hydroxyethyl (meth)-acrylate and polystyrene macromonomer, copolymersof benzyl (meth)acrylate, (meth)acrylic acid, 2-hydroxypropyl(meth)acrylate and polystyrene macro monomer, copolymers of benzyl(meth)acrylate, (meth)acrylic acid, 2-hydroxy-3-phenoxypropyl(meth)acrylate and polymethyl (meth)acrylate macromonomer, copolymers ofmethyl (meth)acrylate, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylateand polystyrene macromonomer, copolymers of benzyl (meth)-acrylate,(meth)acrylic acid, 2-hydroxyethyl (meth)acrylate and polymethyl(meth)acrylate macromonomer, copolymers of N-phenylmaleimide, benzyl(meth)acrylate, (meth)acrylic acid and styrene, copolymers of benzyl(meth)acrylate, (meth)acrylic acid, N-phenyl-maleimide,mono-[2-(meth)acryloyloxyethyl] succinate and styrene, copolymers ofallyl (meth)acrylate, (meth)acrylic acid, N-phenylmaleimide,mono-[2-(meth)acryloyloxyethyl] succinate and styrene, copolymers ofbenzyl (meth)acrylate, (meth)acrylic acid, N-phenyl-maleimide, glycerolmono(meth)acrylate and styrene, copolymers of benzyl (meth)acrylate,[omega]-carboxypolycaprolactone mono(meth)acrylate, (meth)acrylic acid,N-phenyl-maleimide, glycerol mono(meth)acrylate and styrene, andcopolymers of benzyl (meth)-acrylate, (meth)acrylic acid,N-cyclohexylmaleimide and styrene.

A photo curable acrylate oligomer is preferably present in addition tothe photo curable resin. Photo curable acrylate oligomers usable hereininclude dipentaerythritol hexaacryl (DPHA), dipentaerythritolpentaacrylate (DPPA), pentaerythritol triacrylate (PETTA),trimethylol-propane triacrylate (TMPTA), and trimethylolpropanetriacrylate (TMPTA) and the like.

The term transparent pigment refers to a pigment which gives atransparently colored ink when dispersed.

The pigment may be inorganic or preferably organic, for example carbonblack or pigments of the 1-aminoanthraquinone, anthanthrone,anthrapyrimidine, azo, azomethine, quinacridone, quinacridonequinone,quinophthalone, dioxazine, diketopyrrolopyrrole, flavanthrone,indanthrone, isoindoline, isoindolinone, isoviolanthrone, perinone,perylene, phthalocyanine, pyranthrone or thioindigo series, includingthose, where applicable, in the form of metal complexes or lakes, inparticular unsubstituted or partially halogenated phthalocyanines suchas copper, zinc or nickel phthalocyanines,1,4-diketo-3,6-diaryl-pyrrolo[3,4-c]pyrroles, dioxazines,isoindolinones, indanthrones, perylenes and quinacridones. Azo pigmentsmay be, for example, mono- or dis-azo pigments from any known sub-class,obtainable, for example, by coupling, condensation or lake formation.

Notably useful are the pigments described in the Colour Index, includingPigment Yellow 1, 3, 12, 13, 14, 15, 17, 24, 34, 42, 53, 62, 73, 74, 83,93, 95, 108, 109, 110, 111, 119, 120, 123, 128, 129, 139, 147, 150, 151,154, 164, 168, 173, 174, 175, 180, 181, 184, 185, 188, 191, 191:1,191:2, 193, 194 and 199; Pigment Orange 5, 13, 16, 22, 31, 34, 40, 43,48, 49, 51, 61, 64, 71, 73 and 81; Pigment Red 2, 4, 5, 23, 48, 48:1,48:2, 48:3, 48:4, 52:2, 53:1, 57, 57:1, 88, 89, 101, 104, 112, 122, 144,146, 149, 166, 168, 170, 177, 178, 179, 181, 184, 185, 190, 192, 194,202, 204, 206, 207, 209, 214, 216, 220, 221, 222, 224, 226, 242, 248,254, 255, 262, 264, 270 and 272; Pigment Brown 23, 24, 25, 33, 41, 42,43 and 44; Pigment Violet 19, 23, 29, 31, 37 and 42; Pigment Blue 15,15:1, 15:2, 15:3, 15:4, 15:6, 16, 25, 26, 28, 29, 60, 64 and 66; PigmentGreen 7, 17, 36, 37 and 50; Pigment Black 7, 12, 27, 30, 31, 32 and 37;Vat Red 74;3,6-di(3′,4′-dichloro-phenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione,3,6-di(4′-cyano-phenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione and3-phenyl-6-(4′-tert-butyl-phenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione;and mixtures and solid solutions thereof.

Solvent

Normally the compositions according to the invention are dissolved in asuitable solvent before application to the substrate. Examples of suchsolvents include ethylene dichloride, cyclohexanone, cyclopentanone,2-heptanone, gamma-butyrolactone, methyl ethyl ketone, ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethylacetate, 2-ethoxyethyl acetate, 2-ethoxyethanol, diethyl glycol dimethylether, ethylene glycol mono-ethyl ether acetate, propylene glycolmonomethyl ether, propylene glycol monomethyl ether acetate, toluene,ethyl acetate, methyl lactate, ethyl lactate, methylmethoxy propionate,ethylethoxy propionate, methyl pyruvate, ethyl pyruvate, propylpyruvate, N,N-dimethyl-formamide, dimethyl sulfoxide,N-methylpyrrolidone and tetrahydrofuran. Such solvents can be usedindividually or in combinations. Preferred examples thereof are esters,such as 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate,propylene glycol mono-methyl ether acetate, methylmethoxy propionate,ethylethoxy propionate and ethyl lactate.

Photoinitiator:

Any photoinitiator or photolatent catalyst may be used when desired. Thephotoinitiator or photolatent catalyst is not limited. Preferred arephotoinitiators selected from

-   -   1. Alpha-hydroxyketones (AHK), alpha-alkoxyketones        (benzildimethylketals DBK) and alpha-aminoketones (AAK),    -   2. Benzophenones,    -   3. Mono- and bisacylphosphine oxides (BAPO),    -   4. Phenyl-glyoxylates,    -   5. Isopropylthioxanthone (ITX),    -   6. Oxime-esters,    -   7. Aminobenzoates    -   8. Latent acids and bases and blends thereof.

Dispersant

Preferably the first polymerization step is carried out according to thepolymerization reactions a1)

Preferably the second step b) is a transesterification reaction oramidation reaction. Particularly preferred is a transesterificationreaction.

The transesterification preferably comprises the removal of the C₁-C₆alcohol by-product by distillation.

In another embodiment the second step b) is a transesterificationreaction followed by a quaternization.

In a specific embodiment step a1 or a2 of the above described process iscarried out twice and a block copolymer is obtained wherein in the firstor second radical polymerization step the monomer or monomer mixturecontains 50 to 100% by weight, based on total monomers, of a C₁-C₆ alkylor hydroxy C₁-C₆ alkyl ester of acrylic or methacrylic acid and in thesecond or first radical polymerization step respectively, theethylenically unsaturated monomer contains no primary or secondary esterbond.

When a block copolymer is prepared it is preferred that in the firstpolymerization step the monomer or monomer mixture contains from 50 to100% by weight based on total monomers of a C₁-C₆alkyl or hydroxyC₁-C₆alkyl ester of acrylic or methacrylic acid and in the secondpolymerization step the ethylenically unsaturated monomer is4-vinyl-pyridine or pyridinium-ion, 2-vinyl-pyridine or pyridinium-ion,vinyl-imidazole or imidazolinium-ion, dimethylacrylamide,3-dimethylaminopropylmethacrylamide, styrene, α-methyl styrene, p-methylstyrene or p-tert-butyl-styrene.

In a specific embodiment of the invention the block copolymer is agradient block copolymer.

As mentioned above it is mandatory that the polymer or copolymer isprepared by controlled free radical polymerization (CFRP). Solomon etal. in U.S. Pat. No. 4,581,429 have firstly described such processesusing stable free nitroxyl radicals as controlling agents. These are thesteps defined under a1) and a2) above.

U.S. Pat. No. 4,581,429 discloses a free radical polymerization processby controlled or “living” growth of polymer chains, which producesdefined oligomeric homopolymers and copolymers, including block andgraft copolymers. Disclosed is the use of initiators of the partialformula R′R″N—O—X. In the polymerization process the free radicalspecies R′R″N—O• and •X are generated. •X is a free radical group, e.g.a tert.-butyl or cyanoisopropyl radical, capable of polymerizing monomerunits containing ethylene groups.

A variation of the above process is disclosed in U.S. Pat. No. 5,322,912(Xerox) wherein the combined use of a free radical initiator and astable free radical agent of the basic structure R′R″N—O• for thesynthesis of homopolymers and block copolymers is described.

These processes are useful for the preparation of homo-, random-,block-, tapered-, graft- or comb (co)polymers, which have a narrowmolecular weight distribution and hence a low polydispersity index.

For example the structural element

may be part of a cyclic ring system or substituted to form a acyclicstructure.

Suitable nitroxylethers and nitroxyl radicals are principally known fromU.S. Pat. No. 4,581,429 or EP-A-621 878.

Particularly useful are the open chain compounds described in WO98/13392 (Akzo), WO 99/03894 (Ciba) and WO 00/07981 (Ciba), thepiperidine derivatives described in WO 99/67298 (Ciba) and GB 2335190(Ciba) or the heterocyclic compounds described in GB 2342649 (Ciba) andWO 96/24620 (Atochem).

Further suitable nitroxylethers and nitroxyl radicals are described inWO 02/4805 (Ciba) and in WO 02/100831(Ciba).

Nitroxylethers and nitroxyl radicals with more than one nitroxyl groupin the molecule are for example described in U.S. Pat. No.6,573,347(Ciba), WO 01/02345 (Ciba) and WO 03/004471 (Ciba) Thesecompounds are ideally suitable when branched, star or comb (co)polymersare prepared.

In the context of the present invention the terms alkoxyamine andnitroxylether are used as equivalents.

Stable free radicals having a structural element

are for example disclosed in EP-A-621 878 (Xerox).

Examples, such as

are given in WO96/24620 (Atochem).

Preferably the structural element

is part of a 5 or 6-membered heterocyclic ring, which optionally has anadditional nitrogen or oxygen atom in the ring system. Substitutedpiperidine, morpholine and piperazine derivatives are particularlyuseful.

In one preferred embodiment, the structural element

is a structural element of formula (I)

whereinG₁, G₂, G₃, G₄ are independently C₁-C₆alkyl or G₁ and G₂ or G₃ and G₄,or G₁ and G₂ and G₃ and G₄ together form a C₅-C₁₂cycloalkyl group;G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or a group—COOC₁-C₁₈alkyl;X is selected from the group consisting of —CH₂-phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂, (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl and * denotes a valence.

In another preferred embodiment the structural element

is a structural element of formula (II)

whereinG₁, G₂, G₃, G₄ are independently C₁-C₆alkyl or G₁ and G₂ or G₃ and G₄,or G₁ and G₂ and G₃ and G₄ together form a C₅-C₁₂cycloalkyl group;G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or a group—COOC₁-C₁₈alkyl;* denotes a valence.

In particular the structural element of formula (I) is of formula A, Bor O,

whereinR is hydrogen, C₁-C₁₈alkyl which is uninterrupted or interrupted by oneor more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalentradical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, ofa cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or anα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms;R₁₀₁ is C₁-C₁₂alkyl, C₅-C₇cycloalkyl, C₇-C₈aralkyl, C₂-C₁₈alkanoyl,C₃-C₅alkenoyl or benzoyl;R₁₀₂ is C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₂-C₈alkenyl unsubstituted orsubstituted by a cyano, carbonyl or carbamide group, or is glycidyl, agroup of the formula —CH₂CH(OH)-Z or of the formula —CO-Z or —CONH-Zwherein Z is hydrogen, methyl or phenyl;G₆ is hydrogen andG₅ is hydrogen or C₁-C₄alkyl,G₁ and G₃ are methyl and G₂ and G₄ are ethyl or propyl or G₁ and G₂ aremethyl and G₃ andG₄ are ethyl or propyl; andX is selected from the group consisting of —CH₂-phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂, (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl.The above compounds and their preparation are described in GB2335190 andGB2361235.

Another preferred group of nitroxylethers are those of formula (Ic),(Id), (Ie), (If), (Ig) or (Ih)

whereinR₂₀₁, R₂₀₂, R₂₀₃ and R₂₀₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₂₀₅,C₂-C₁₈alkyl which is interrupted by at least one O atom and/or NR₂₀₅group, C₃-C₁₂cycloalkyl or C₆-C₁₀aryl or R₂₀₁ and R₂₀₂ and/or R₂₀₃ andR₂₀₄ together with the linking carbon atom form a C₃-C₁₂cycloalkylradical;R₂₀₅, R₂₀₆ and R₂₀₇ independently are hydrogen, C₁-C₁₈alkyl orC₆-C₁₀aryl;R₂₀₈ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl which are substituted by oneor more OH, halogen or a group —O—C(O)—R₂₀₅, C₂-C₁₈alkyl which isinterrupted by at least one O atom and/or NR₂₀₅ group, C₃-C₁₂cycloalkylor C₆-C₁₀aryl, C₇-C₉phenylalkyl, C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl,—O—C₁-C₁₈alkyl or —COOC₁-C₁₈alkyl;R₂₀₉, R₂₁₀, R₂₁₁ and R₂₁₂ are independently hydrogen, phenyl orC₁-C₁₈alkyl; andX is selected from the group consisting of —CH₂-phenyl, CH₃CH-phenyl,(CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl.

More preferably in formula (Ic), (Id), (Ie), (If), (Ig) and (Ih) atleast two of R₂₀₁, R₂₀₂, R₂₀₃ and R₂₀₄ are ethyl, propyl or butyl andthe remaining are methyl; or

R₂₀₁ and R₂₀₂ or R₂₀₃ and R₂₀₄ together with the linking carbon atomform a C₅-C₆cycloalkyl radical and one of the remaining substituents isethyl, propyl or butyl.

Most preferably X is CH₃CH-phenyl.

The above compounds and their preparation are described in GB 2342649.

Further suitable compounds are the 4-imino compounds of formula (III) or(III′)

whereinG₁₁, G₁₂, G₁₃ and G₁₄ are independently C₁-C₄alkyl or G₁₁ and G₁₂together and G₁₃ and G₁₄ together, or G₁₁ and G₁₂ together or G₁₃ andG₁₄ together are pentamethylene;G₁₅ and G₁₆ are each independently of the other hydrogen or C₁-C₄alkyl;X is as defined above;k is 1,2,3, or 4Y is O or NR₃₀₂ or when k is 1 and R₃₀₁ represents alkyl or aryl Y isadditionally a direct bond;R₃₀₂ is H, C₁-C₁₈alkyl or phenyl;if k is 1R₃₀₁ is H, straight or branched C₁-C₁₈alkyl, C₃-C₁₈alkenyl orC₃-C₁₈alkinyl, which may be unsubstituted or substituted, by one or moreOH, C₁-C₈alkoxy, carboxy, C₁-C₈alkoxycarbonyl; C₅-C₁₂cycloalkyl orC₅-C₁₂cycloalkenyl;phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy,carboxy, C₁-C₈alkoxycarbonyl;—C(O)—C₁-C₃₆alkyl, or an acyl moiety of a α,β-unsaturated carboxylicacid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having7 to 15 carbon atoms;—SO₃ ⁻Q⁺, —PO(O⁻Q⁺)₂, —P(O)(OC₁-C₈alkyl₂)₂, —P(O)(OH₂)₂, —SO₂—OH,—SO₂—C₁-C₈alkyl, —CO—NH—C₁-C₈alkyl, —CONH₂, COO—C₁-C₈alkyl₂, COOH orSi(Me)₃, wherein Q⁺ is H⁺, ammonium or an alkali metal cation;if k is 2R₃₀₁ is C₁-C₁₈alkylene, C₃-C₁₈alkenylene or C₃-C₁₈alkinylene, which maybe unsubstituted or substituted, by one or more OH, C₁-C₈alkoxy,carboxy, C₁-C₈alkoxycarbonyl; or xylylene; or R₃₀₁ is a bisacyl radicalof an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or acycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;if k is 3,R₃₀₁ is a trivalent radical of an aliphatic, cycloaliphatic or aromatictricarboxylic acid;andif k is 4, R₃₀₁ is a tetravalent radical of an aliphatic, cycloaliphaticor aromatic tetracarboxylic acid.

Preferably G₁₆ is hydrogen and G₁₅ is hydrogen or C₁-C₄alkyl, inparticular methyl, and G₁₁ and G₁₃ are methyl and G₁₂ and G₁₄ are ethylor propyl or G₁₁ and G₁₂ are methyl and G₁₃ and G₁₄ are ethyl or propyl.

The 4 imino compounds of formula III can be prepared for exampleaccording to E. G. Rozantsev, A. V. Chudinov, V. D. Sholle.: Izv. Akad.Nauk. SSSR, Ser. Khim. (9), 2114 (1980), starting from the corresponding4-oxonitroxide in a condensation reaction with hydroxylamine andsubsequent reaction of the OH group. The compounds are described WO02/100831 (Ciba)

In particular the structural element of formula (II) is of formula A′,B′ or O′,

whereinR is hydrogen, C₁-C₁₈alkyl which is uninterrupted or interrupted by oneor more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalentradical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, ofa cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or anα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms;R₁₀₁ is C₁-C₁₂alkyl, C₅-C₇cycloalkyl, C₇-C₈aralkyl, C₂-C₁₈alkanoyl,C₃-C₅alkenoyl or benzoyl;R₁₀₂ is C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₂-C₈alkenyl unsubstituted orsubstituted by a cyano, carbonyl or carbamide group, or is glycidyl, agroup of the formula —CH₂CH(OH)-Z or of the formula —CO-Z or —CONH-Zwherein Z is hydrogen, methyl or phenyl;G₆ is hydrogen andG₅ is hydrogen or C₁-C₄alkyl, G₁ and G₃ are methyl and G₂ and G₄ areethyl or propyl or G₁ and G₂ are methyl and G₃ and G₄ are ethyl orpropyl.

The alkyl radicals in the various substituents may be linear orbranched. Examples of alkyl containing 1 to 18 carbon atoms are methyl,ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl,2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as forexample propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl,3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl,n-2-octadecenyl or n-4-octadecenyl. Preferred is alkenyl with 3 to 12,particularly preferred with 3 to 6 carbon atoms.

Alkinyl with 3 to 18 is a linear or branched radical as for examplepropinyl (—CH—C≡CH), 2-butinyl, 3-butinyl, n-2-octinyl, orn-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularlypreferred with 3 to 6 carbon atoms.

Examples for hydroxy substituted alkyl are hydroxy propyl, hydroxy butylor hydroxy hexyl.

Examples for halogen substituted alkyl are dichloropropyl,monobromobutyl or trichlorohexyl.

C₂-C₁₈alkyl interrupted by at least one O atom is for example—CH₂—CH₂—O—CH₂—CH₃, —CH₂—CH₂—O—CH₃— or—CH₂—CH₂—O—CH₂—CH₂—CH₂—O—CH₂—CH₃—.

It is preferably derived from polyethlene glycol. A general descriptionis —((CH₂)_(a)—O)_(b)—H/CH₃, wherein a is a number from 1 to 6 and b isa number from 2 to 10.

C₂-C₁₈alkyl interrupted by at least one NR₂₀₅ group may be generallydescribed as —((CH₂)_(a)—NR₂₀₅)_(b)—H/CH₃, wherein a, b and R₂₀₅ are asdefined above.

C₃-C₁₂cycloalkyl is typically, cyclopropyl, cyclopentyl,methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl ortrimethylcyclohexyl.

C₆-C₁₀ aryl is e.g. phenyl or naphthyl, but also comprised areC₁-C₄alkyl substituted phenyl, C₁-C₄alkoxy substituted phenyl, hydroxy,halogen or nitro substituted phenyl. Examples for alkyl substitutedphenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene orisopropylbenzene. Halogen substituted phenyl is e.g. dichlorobenzene orbromotoluene.

Alkoxy substituents are typically methoxy, ethoxy, propoxy or butoxy andtheir corresponding isomers.

C₇-C₉-phenylalkyl is benzyl, phenylethyl or phenylpropyl.

C₅-C₁₀heteroaryl is for example pyrrol, pyrazol, imidazol, 2,4,dimethylpyrrol, 1-methylpyrrol, thiophene, furane, furfural, indol,cumarone, oxazol, thiazol, isoxazol, isothiazol, triazol, pyridine,α-picoline, pyridazine, pyrazine or pyrimidine.

If R is a monovalent radical of a carboxylic acid, it is, for example,an acetyl, propionyl, butyryl, valeroyl, caproyl, stearoyl, lauroyl,acryloyl, methacryloyl, benzoyl, cinnamoyl orβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

C₁-C₁₈alkanoyl is for example, formyl, propionyl, butyryl, octanoyl,dodecanoyl but preferably acetyl and C₃-C₅alkenoyl is in particularacryloyl.

In particular polymerization process a1) is very suitable. When processa1) is used the nitroxylether according to the structures outlined abovesplits between the O—X bond. The regulating fragment in formula (I)corresponds to the O—N fragment and the initiating fragment (In)corresponds to the C centered radical of the group X.

Particularly suitable nitroxylethers and nitroxyl radicals are those offormulae

In a very specific embodiment of the invention, the polymer or copolymeris prepared with a compound of formula (O1)

Preferably the initiator compound is present in an amount of from 0.01mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-% to 20mol-% and most preferred in an amount of from 0.1 mol-% to 10 mol-%based on the monomer or monomer mixture.

When monomer mixtures are used mol % is calculated on the averagemolecular weight of the mixture.

When the process according to route a2) is chosen, the free radicalinitiator is preferably an azo compound, a peroxide, perester or ahydroperoxide.

Specific preferred radical sources are 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methyl-butyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride,2,2′-azobis{2-methyl-N-[1,1-bis(hydroxy-methyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxy-ethyl]propionamide;acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate,t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate,t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoylperoxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide,bis(2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetylperoxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate,bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butylpermaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethyl-cyclohexane,1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate,t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butylperacetate, t-amyl perbenzoate, t-butyl perbenzoate,2,2-bis(t-butylperoxy) butane, 2,2 bis(t-butylperoxy) propane, dicumylperoxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy3-phenylphthalide, di-t-amyl peroxide, α, α′-bis(t-butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane,di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthanehydroperoxide, pinane hydro-peroxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

The radical source is preferably present in an amount of from 0.01 mol-%to 30 mol-%, more preferred in an amount of from 0.1 mol-% to 20 mol-%and most preferred in an amount of from 0.5 mol-% to 10 mol-% based onthe monomer or monomer mixture.

The molar ratio of the radical source to the nitroxyl radical may befrom 1:10 to 10:1, preferably from 1:5 to 5:1 and more preferably from1:2 to 2:1.

The polymer or copolymer can also be prepared in a controlled way byatom transfer radical polymerization (ATRP). This type of polymerizationis, for example, described in WO 96/30421.

Reversible addition fragmentation chain transfer polymerization (RAFT)is also a well known controlled free radical polymerization techniqueand for example described in WO 98/01478, WO98/58974, WO 99/31144, WO99/05099, WO 02/094887, WO 02/26836, WO 01/42312, WO 00/75207, and WO99/35177.

The polymer or copolymer prepared according to steps a1) or a2) haspreferably a polydispersity index of 1.0 to 2.2, more preferably from1.1 to 1.9 and most preferably from 1.1 to 1.5.

As already mentioned above the second reaction step b), i.e. the polymeranalogous reaction, is a transesterification reaction, an amidation,hydrolysis or anhydride modification or a combination thereof, andoptionally in addition by quaternization.

Hydrolysis means the cleavage of an ester bond under alkaline or acidicconditions and can be carried out when the polymer or copolymer containsester functionalities. The degree of hydrolysis may vary in a wide rangeand depends on reaction time and conditions. For example 5 to 100%,preferably 10% to 70% of the ester functionalities may be hydrolized, toform the free acid group, from which also a salt can be prepared. Themetal ion is preferably an alkali metal ion, such as Li⁺, Na⁺ or Ka⁺ oran ammonium cation, such as NH₄ ⁺ or NR₄₀₄, wherein R₄₀₄ is hydrogen orC₁-C₁₈alkyl.

Anhydride modification can be carried out when the polymer or copolymercontains hydroxyl functionalities. The hydroxyl functionalities come forexample from hydroxyl functional monomers, such as hydroxyethyl acrylateor methacrylate. Virtually all aliphatic or aromatic anhydrides can beused in the modification process. Examples for anhydrides are maleicacid anhydride, pyromelitic acid anhydride, cyclohexyldiacid anhydride,succinic acid anhydride, camphoric acid anhydride.

Transesterification means to replace the alcohol radical in an estergroup of the polymer or copolymer by another alcohol radical. Preferablythe alcohol radical to be replaced is methanol, ethanol, propanol orbutanol. Typically the transesterification reaction is carried out atelevated temperatures, typically 70-200° C., by reacting the CFRPpolymer with the corresponding alcohol using well-known catalysts, suchas tetra-isopropyltitanate, tetrabutyltitanate, alkali- or earth alkalialcoholates like NaOMe or LiOMe. Typically the low boiling productalcohol is removed from the transterification reaction mixture bydistillation. If needed, catalyst residues may be removed by adsorptionor extraction or otherwise processed or inactivated by known methods,like hydrolysis with water or acids.

The choice of the replacing alcohol is important. The replacing alcoholcontrols the properties of the resulting copolymer.

Using a polar replacing alcohol such as alcohols having e.g. thefollowing formula R—[O—CH₂—CH₂—], —OH, e.g. methoxypoly4ethylene glycol(MPEG-OH), it is possible to obtain a water soluble resulting polymer.Of course the solubility depends on the amount of transesterifiedmonomer units. At least 40% of the units should be transesterified toobtain the desired effect.

If solubility in organic solvents is required non polar alcohols likehigher molecular weight branched aliphatic alcohols can be beneficial.

If polymers with low surface tension are desired, alcohols containingsiloxane groups are preferred, e.g. with the following formula

or partly or fully fluorinated primary alcohols can be used instead orin addition.

If a solid copolymer is required, solid alcohols or polar alcohols whichare able to raise the glass transition temperature (Tg) or impart sidechain crystallinity should be used. An example is behenyl alcohol.

The replacing alcohol radical is typically an aliphatic C₆-C₃₆alcohol ora precursor of an alcohol, having at least one —OH group. The alcoholmay also be interrupted by 1 to 20 O or N atoms or substituted byhalogen, perfluoralkyl, NH₂, NH(C₁-C₁₈alkyl), N(C₁-C₁₈alkyl)₂,COO(C₁-C₁₈alkyl), CON(C₁-C₁₈alkyl)₂, CONH(C₁-C₁₈alkyl), CONH₂, COOH,COO—, O(C₁-C₁₈alkyl) or with a Si, P or S containing group, for examplealkylhydroxysilicones. The alcohol may also contain heterocyclic ringstructures, such as 1-(2-hydroxyethyl)-2-pyrrolidinone,1-(2-hydroxyethyl)-2-imidazolidinone, 2-(2-hydroxyethyl)pyridine,N-2-hydroxyethyl)phtalimide, 4-(2-hydroxyethyl)morpholine,1-(2-hydroxyethyl)piperazine, N-hydroxymethylphthalimide,3-hydroxymethylpyridine or (4-pyridyl)-1-propanol.

The alcohols, which are interrupted by O or N atoms are not limited to36 C atoms. These can be oligomeric or polymeric alcohols also. Examplesof alcohols interrupted by O atoms are methoxypolyethyleneglycols or allkinds of adducts of ethyleneoxide and/or propylene-oxide (EO/PO). SuchEO/PO-adducts can be random or block type structures.

Preferably the alcohol is an unsubstituted linear or branchedC₈-C₃₆alkyl mono alcohol or a mono alcohol derived from ethylenoxide,propylenoxide or mixtures thereof with up to 100 C atoms. Especiallypreferred is MPEG-OH.

It is also possible to use fatty acid alcohol ethoxylates,alkylphenolethoxylates, alkoxylates of all kinds of monofuntionalalcohols or phenols or secondary amines.

Preferably the alkoxylate is an ethoxylate of a primary alcohol oralkylphenol of structure (A):

R—[O—CH₂—CH₂—]_(n)—OH  (A)

wherein R is saturated or unsaturated, linear or branched chain alkylwith 1-22 carbon atoms, or alkylaryl or dialkylaryl with up to 24 carbonatoms and n is 1 to 50.

Referring to an other embodiment the alcohol is an unsubstituted linearor branched C₈-C₃₆alkyl mono alcohol or mixtures thereof. An example isa mixture of iso C₁₂-C₁₅ alcohol. Non-polar polymers or copolymers areobtained.

In another embodiment, the macroalcohol is a primary OH-functionalsilicone oligomer. Preferred are polydimethylsilicone oligomers ofstructure (B):

whereinR is C₁-C₁₈alkyl, phenyl or C₇-C₁₅aralkyl; n is 1 to 50 and R′ is alinking group with 1 to 20 carbon atoms.

Typical linking groups are C₁-C₁₈alkylene, phenylene or C₁-C₁₈alkyleneinterrupted by 1 to 6 oxygen atoms.

In another embodiment the alcohol is a partly or fully fluorinatedprimary alcohols. Examples of commercial fluorinated alcohol mixturesare: Zonyl BA®, Zonyl BA-L®, Zonyl BA-LD®, Zonyl BA-N® from Du Pont.

Aryl is phenyl or naphthyl, preferably phenyl.

Precursors of alcohols are for example macroalcohols, such aspoly-ε-caprolactone oligomers or ε-caprolactone adducts and similarlactone adducts (e.g. based on valerolactone) or mixed adducts ofε-caprolactone and valerolactone. Typical lactone adducts are adducts ofε-caprolactone to long chain fatty alcohols of structure:

R—[O—CO—CH₂—CH₂—CH₂—CH₂—CH₂—]_(n)—OH

wherein R is saturated or unsaturated, linear or branched chain alkylwith 8-22 carbon atoms or alkylaryl or dialkylaryl with up to 24 carbonatoms and n is 1 to 50.

It is also possible to use macroalcohols based on polyolefins, whichhave typically molecular weights up to 5000, preferably up to 2000.

Yet another embodiment are unsaturated alcohols containing carbon-carbondouble bonds or carbon triple bonds. An example is oleyl alcohol.Regarding triple bond preferred are primary alkinols like propargylalcohol and higher homologues like alkylsubstituted propargylalcohol.

Preferably the alcohol is a monoalcohol and is a primary or secondaryalcohol. Most preferred are primary alcohols or alcohol mixtures likeLial 125.

Preferably the alcohol or alcohol mixture is non-volatile and has aboiling point or range of at least 100° C., more preferably of at least200° C.

The quaternization means the formation of ammonium salts of the aminogroup present in amino monomers selected from the group consisting ofamino substituted styrene, (C₁-C₄alkyl)₁₋₂amino substituted styrene,N-mono-(C₁-C₄alkyl)₁₋₂aminoC₂-C₄alkyl(meth)-acrylamide andN,N-di-(C₁-C₄alkyl)₁₋₂amino-C₂-C₄alkyl(meth)acrylamide, vinylpyridine orC₁-C₄alkyl substituted vinylpyridine, vinylimidazole and C₁-C₄alkylsubstituted vinylimidazole.

Representative N-mono-(C₁-C₄alkyl)₁₋₂amino-C₂-C₄alkyl(meth)acrylamideand N,N-di-(C₁-C₄alkyl)₁₋₂amino-C₂-C₄alkyl(meth)acrylamide are2-N-tert-butylamino- or 2-N,N-dimethyl-aminoethylacrylamide or2-N-tert-butylamino- or 2-N,N-dimethylaminopropylmethacrylamide.

Quaternization is effected with active alkyl halides or alkyl esters oforganic sulphonic acids. In this case examples of preferred salt formingcomponents are benzylchloride, 2-chlorobenzylchloride,4-chlorobenzylchloride, 2,4-dichlorobenzylchloride, p-toluene sulphonicacid methyl ester, p-toluene sulphonic acid ethyl ester, especiallypreferred 4-chlorobenzylchloride.

Under the term amidation there is understood the modification of theester function of a polyacrylate with an amine under the formation of anamide bond. Preferably the amine is a monofunctional primary orsecondary amine, most preferably a primary aliphatic or aromatic amine.The reaction of the amine with the ester function of the CFRP polymer istypically conducted at elevated temperatures of 70-200° C., optionallyin presence of catalysts. In a preferred process, the resulting alcoholis removed during the amidation reaction by distillation.

Preferably the amine has a high boiling point or boiling range of above100° C.

Typical amines are primary aliphatic or aromatic amines with up to 36carbon atoms, linear, branched or cyclic. The amine may containheteroatoms O or N.

In a preferred embodiment there are oligomers and macroamines with asingle primary amine and molecular weights of up to 5000. Typicalexamples are primary amine end-functional alkoxylates. Especiallypreferred are also primary amines containing other polar groups likeether, ester and amide groups.

In principal the monomer in step a1 or a2 can be selected from isoprene,1,3-butadiene, α-C₅-C₁₈alkene, 4-vinyl-pyridine or pyridinium-ion,2-vinyl-pyridine or pyridinium-ion, vinyl-imidazole orimidazolinium-ion, dimethylacrylamide,3-dimethylaminopropylmethacrylamide, styrene, α-methyl styrene, p-methylstyrene, p-tert-butyl-styrene or a compound of formulaCH₂═C(R_(a))—(C═Z)-R_(b), wherein R_(a) is hydrogen or C₁-C₄alkyl, R_(b)is NH₂, O⁻(Me⁺), unsubstituted C₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interruptedby at least one N and/or O atom, or hydroxy-substituted C₁-C₁₈alkoxy,unsubstituted C₁-C₁₈alkylamino, di(C₁-C₁₈alkyl)amino,hydroxy-substituted C₁-C₁₈alkylamino or hydroxy-substituteddi(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂An⁻;

An⁻ is a anion of a monovalent organic or inorganic acid;Me is a monovalent metal atom or the ammonium ion.Z is oxygen or sulfur

Preferred are 3-dimethylaminopropylmethacrylamide, 2-vinyl-pyridine,4-vinyl-pyridine, hydroxyethylacrylate, hydroxyproylacrylate,n-butylacrylate, styrene.

Examples for R_(b) as C₂-C₁₀₀alkoxy interrupted by at least one O atomare of formula

wherein R_(c) is C₁-C₂₅alkyl, phenyl or phenyl substituted byC₁-C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1 to 50.These monomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

An⁻, wherein An⁻ and R_(a) have the meaning as defined above and R_(e)is methyl, benzyl or benzoylbenzyl. An⁻ is preferably Cl⁻, Br⁻ or⁻O₃S—O—CH₃.

Further acrylate monomers are

Me⁺, Me⁺ is an alkali metal cation or the ammonium cation. Useful arealso silicone functional (meth)acrylates.

Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, glycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and Z isoxygen.

For example the ethylenically unsaturated monomer is selected from thegroup consisting of ethylene, propylene, n-butylene, i-butylene,styrene, substituted styrene, conjugated dienes, acrolein, vinylacetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acid-anhydrides, (alkyl)acrylic acid salts,(alkyl)acrylic esters, (alkyl)acrylonitriles, (alkyl)acryl-amides, vinylhalides or vinylidene halides.

For instance the ethylenically unsaturated monomer is styrene,substituted styrene, methyl-acrylate, ethylacrylate, butylacrylate,isobutylacrylate, tert. butylacrylate, hydroxyethyl-acrylate,hydroxypropylacrylate, dimethylaminoethylacrylate, methyl(meth)acrylate,ethyl-(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl (meth)-acrylate, dimethylaminoethyl(meth)acrylate,acrylonitrile, methacrylonitrile, acrylamide, meth-acrylamide ordimethylaminopropyl-methacrylamide.

Very suitable monomers are for example styrene, C₁-C₈alkylesters ofacrylic or methacrylic acid, such as n-butylacrylate or methacrylate,acrylonitrile or methacrylonitrile, in particular styrene, acrylonitrileand n-butylacrylate.

It is also possible to use mixtures of the afore mentioned monomers, inparticular styrene/acrylonitrile, styrene/butylacrylate,styrene/methylmethacrylate and styrene/butylmethacrylate

Preference is given to a polymerizable composition wherein theethylenically unsaturated monomer is a compound of formulaCH₂═C(R_(a))—(C═Z)-R_(b), wherein Z is O or S;

R_(a) is hydrogen or C₁-C₄alkyl;R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy,C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom, orhydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂An⁻;An⁻ is a anion of a monovalent organic or inorganic acid;Me is a monovalent metal atom or the ammonium ion.

All possible polymer chain structures are comprised: e.g. linear orbranched. If the monomers are selected from chemically differentmonomers, all possible monomer sequence structures are comprised, e.g.random-, blocklike, multiblock-, tapered- or gradient arrangement of thedifferent monomers.

Under gradient polymers or gradient arrangement there are understoodblock copolymers, which are prepared in such a way, that theintersection between the two blocks is not a sharp boundary, butrepresents a continuous transition from one type of monomer to anothertype of monomer, i.e. both monomers extending to both blocks. This typeof polymers can be obtained when the polymerization process is carriedout for example in one step using monomers of different copolymerizationparameters or by a multistep procedure, in which the monomer compositionis stepwise changed by addition of appropriate amounts of another typeof monomer. Another preferred procedure for the synthesis of gradientpolymers is by using continuous feed processes, in which for example thecontrolled polymerization is started with a first monomer and beforecomplete conversion, a second monomer is continuously fed to thereaction mixture, thus realizing a continuous transition along thepolymer chains.

When step a1 or a2 of the process is carried out twice and a blockcopolymer is obtained for example the monomer or monomer mixture of thefirst radical polymerization contains from 50 to 100% by weight based ontotal monomers of a C₁-C₄ alkyl or hydroxyalkyl ester of acrylic ormethacrylic acid and the second radical polymerization contains amonomer or monomer mixture possessing no primary or secondary esterbond.

Suitable monomers for the second radical polymerization do not react inthe postmodification reaction, such as vinyl aromatic monomers orvinyl-aza-heterocycles.

Examples are 4-vinyl-pyridine(pyridinium-ion),2-vinyl-pyridine(pyridinium-ion), vinyl-imidazole(imidazolinium-ion),dimethylacrylamide, acrylnitrile, 3-dimethylaminopropyl-methacryl-amide,styrene or substituted styrenes.

Naturally the sequence of the first and second radical polymerizationcan also be reversed.

When a block copolymer is prepared it is preferred that in the firstpolymerization the monomer or monomer mixture contains from 50 to 100%by weight based on total monomers of a C₁-C₆ alkyl or hydroxyalkyl esterof acrylic or methacrylic acid and in the second polymerization theethylenically unsaturated monomer is 4-vinyl-pyridine or pyridinium-ion,2-vinyl-pyridine or pyridinium-ion, vinyl-imidazole orimidazolinium-ion, dimethylacrylamide,3-dimethylaminopropylmethacrylamide, styrene, α-methyl styrene, p-methylstyrene or p-tert-butyl-styrene.

In another specific embodiment of the invention, the monomers of thecontrolled polymer prepared according to a first step a1) or a2) containaminic or acid groups, is than modified in a second step by atransesterification reaction, an amidation, hydrolysis or anhydridemodification and thereafter the aminic or acid groups of the modifiedcontrolled polymer are converted to salt structures by reaction with asalt forming component. Typical salt forming components for amino groupsare for example organic or inorganic acids or alkylhalogenides,especially such salt forming components, which are based on organiccyclic acids or cyclic alkylhalogenides. Typical examples of such saltforming components are described in EP 1275689 (Ciba) and WO 03/046029(Ciba)

Typical salt forming components for acid groups on the modifiedcontrolled polymer are inorganic bases, such as NaOH, KOH, NH4OH orvolatile aminoalcohols, such as 2-di-methylaminoethanol or2-amino-2-methylpropanol (AMP), which are frequently used in coatings.

It is also possible to choose the monomers in the polymerization stepsand the post modification reaction in such a way, that a lower criticalsolution temperature (LCST) in water or water rich solvent mixtures isobtained for the final polymer or copolymer.

This means, that the polymer or copolymer shows a good solubility at lowtemperatures and a decreasing solubility at high temperatures. Thiseffect is for example described by Hammouda, B.; Ho, D.; Kline, S inMacromolecules (2002), 35(22), 8578-8585).

The invention further relates to a method for producing a color filter,which comprises coating the color filter composition described above ona substrate, followed by exposure and development.

A “substrate” means any carrier material adapted to be coated withphotoresist layers for the purpose of exposure. For this purposefrequently glass plates are used, which may be colored black or coated.Furthermore, plastic foils or metal foils that are already provided witha grating image, preferably in the form of an embossing, are suitable assubstrates.

Examples of the coating of the photosensitive film include slit coatingusing a coating device having slit type nozzles, slit-and-spin coatingthat first coats using a nozzle and then coats using a spin coater, diecoating, and curtain flow coating. Of these coating methods, theslit-and-spin coating is preferred. After the coating, thephotosensitive resin composition may be prebaked to remove volatileingredients such as solvents, thereby forming the photosensitive resinfilm containing substantially no volatile ingredient. The photosensitiveresin film may have a thickness of about 1 to 10 μm.

Next, the photosensitive film is subjected to a first exposure through amask. The mask has a pattern suitable for the function of the hardenedresin pattern.

The photoresist resin film is then developed by puddle development,immersion development, or spray development. The development may beperformed by using an alkaline aqueous solution. The alkaline aqueoussolution contains an inorganic alkaline compound or an organic alkalinecompound.

The invention further relates to the use of a dispersant as disclosedabove in a color filter composition.

EXAMPLES

The following examples illustrate the invention.

Materials Use and their Abbreviations:Monomers: butylacrylate (BA), hydroxyethylacrylate (HEA),hydroxypropylacrylate (HPA), 4-vinyl-pyridine (4-VP), styrene (S),dimethylaminopropyl methacrylate (DMAPMA)Modification agents: cyclohexylacid anhydride (CHAA), succinic acidanhydride (SAA), methoxy-poly-ethyleneglycole (MPEG 550-OH), Lial 125 isa mixture of iso-C₁₂-C₁₅ alcohols, available from CondeaSolvents: methoxypropylacetate (MPA), Xylene, methoxypropanol (MP),polystyrene (PS), tetrahydrofurane (THF), polyethyleneoxide (POE/PEG),methoxytriglycol (MTG).

ATRP process: initiator is 2-bromoethylpropionate (MBP), the catalyst isCuBr/CuBr₂, the ligand is N,N,N′,N″,N″-pentamethyldiethyltriamine(PMDETA).

NOR Initiator/regulator is compound O1

which is prepared according to GB 2335190.

All other materials are commercially available and were used asreceived.

A) Preparation of Polymers and Copolymers Example A1 Synthesis of aLinear Polymer Poly(BA)

In a 3-necked 1000 ml round bottom flask with magnetic stirring bar,cooler, thermometer, dropping funnel 150.10 g n-butylacrylate (n-BA,128.17 g/mol), 8.55 g compound O1 (317.48 g/mol) and 122.13 g of MPAwere added, three times degassed with N₂/vacuum and polymerized at 135°C. under N₂ until a conversion of around 8 mol % is reached. 338.89 g ofn-BA is slowly added to the reaction with the dropping funnel andpolymerized at 135° C. under N₂ until a conversion of around 48 mol %.Residual monomers and solvents were distilled off at 80° C. and 12 mbar.

Yield 47%, GPC (THF, PS-Standard, Mn=7800 g/mol, PD=1.27), liquid.

According to analysis via ¹H-NMR, the degree of polymerization is 75.

Example A2 Synthesis of a Linear Block Copolymer Poly(n-BA-b-4VP)

In a 3-necked 500 ml round bottom flask with magnetic stirring bar,cooler, thermometer 214.18 g poly(n-BA) of example A1, 70.90 g4-vinylpyridine (4-VP, 105.14 g/mol) and 79.70 g of MPA are added, threetimes degassed with N₂/vacuum and polymerized at 125° C. under N₂ for 8h. Residual monomers and solvents are distilled off at 80° C. and 12mbar.

Yield 85%, GPC (THF, PS-Standard, Mn=8600 g/mol, PD=1.24), liquid.

According to analysis via ¹H-NMR, the degree of polymerization is:P(BA-b-4VP)=75-b-14.

Example A3 Poly(n-BA-MPEGA-b-4-VP)

Transesterification Using MPEG-OH

In a 500 mL flask equipped with a magnetic stirring bar, distillationcolumn with dry ice acetone cooling 92.8 g of Poly(n-BA-b-4-VP)according to example A2 in 107.2 g of Xylene and 114.7 g of MPEG-OH(Mn=550 g/mol) are added and dried by azeotropic distillation of thexylene. Three portions of 0.36 g of tera(isopropyl)orthotitanate areadded during 3 h at 190-205° C. The formed n-Butanol is distilled of atlow pressure.

187.7 g of Poly(n-BA-MPEGA-b-4-VP) are obtained. Mn=17500 g/mol,PDI=1.6, OH-value=0.05 meq/g. Anaylsis via GPC as well as 1H_NMRindicate almost quantitative conversion of the MPEG-OH.

The resulting polymer is well soluble in water and shows an LCST-typesolution behaviour (LCST=lower critical solution temperature), i.e. thesolubility of the polymer decreases with increasing temperature). A 35wt % solution of the endproduct polymer in water is a clear solution atroom temperature, but becomes turbid at elevated temperatures above 70°C.

The resulting polymer also formed clear 10 wt % solutions in followingorganic solvents: butyl acetate, methoxypropylacetate, methoxypropanol,butylglycol and xylene.

Example A4 Synthesis of a Linear Polymer Poly(BA)

In a 6 liter reactor equipped with stirrer, cooler, thermometer, andmonomer feed pumps 1519 g n-Butylacrylate, 209 g compound O1 were added,three times degassed with N₂/vacuum and heated to 115° C. under N₂,where a continuous feed of n-butylacrylate was started over 4 hours andat the same time the reaction mass slowly heated to 135° C. After theend of the monomer feed, the reaction mass was further reacted for 5 huntil a solids content of 55% was reached. Afterwards, the non reactedmonomer was removed by vacuum distillation.

2812 g of Poly(n-BA) are obtained as liquid polymer, Mn=4554, PDI=1.18

According to analysis via ¹H-NMR, the degree of polymerization is:P(nBA)=35.

Example A5 Synthesis of a Linear Block Copolymer Poly(n-BA-b-4VP)

In the same reactor as in Ex. A4, 2674 g of polymer A4 were loadedtogether with 1133 g 4-vinylpyridine and heated under N₂ to 135° C. andreacted for 3.5 h until a solids content of 91% was reached. Thispolymer was used for subsequent transesterifications without furtherremoval of non-reacted 4-vinylpyridine.

3732 g of Polymer P(nBA-b-4VP) were isolated from the reactor, Mn=4779,PDI=1.19 According to analysis via ¹H-NMR, the degree of polymerizationis: P(nBA-b-4VP)=35-b-14.

Example A6 Synthesis of Block Copolymer Poly(n-BA-MPEGA-b-4-VP)Transesterification Using MPEG-OH

In the same reactor as in example A4, 3730 g of the polymer A5 wereloaded together with 3503 g of MPEG-OH (M=550 g/mol) and subjected tovacuum degassing at 130° C. for one hour to remove non-reacted4-vinylpyridine. 12.0 g of LiOMe-solution (10 wt % lithium methanolatein methanol were added slowly and the transesterification started bydistilling off n-Butanol at 130° C. and reduced pressure. Additional 5portions of catalyst were added after every hour: 2×12.0 g andadditional 3×14.5 g of LiOMe-solution. After 6 h the reaction wascompleted by collecting the calculated amount of n-butanol.

6322 g of viscous polymer were obtained; Mn=8829, PDI=1.36

Anaylsis via GPC as well as 1H_NMR indicate almost quantitativeconversion of the MPEG-OH.

According to analysis via ¹H-NMR, the degree of polymerization is:P[(nBA-MPEGA)-b-4VP]=(23-12)-b-14.

OH-number titration: 0.20 meq/gAmine number titration: 69 mg KOH/gThe 50 wt % solids solution in water displays an LCST of 67° C.

Aside from water, the polymer A6 gives clear solutions 10 wt % infollowing organic solvents: butyl acetate, methoxypropylacetate,methoxypropanol, butylglycol and xylene.

For testing as pigment dispersant part of the polymer A6 was dissolvedin water to give a clear 50 wt % solids solution, other parts of thepolymer were dissolved in various other organic solvents.

Example A7 Synthesis of a Random Copolymer Poly(n-BA-MPEGA)

In the same reactor as in example A4 were loaded 500 g of a poly(n-BA)(Mn=8304, PDI=1.21), which was made analog polymer A4 and 500 g ofMPEG-OH (M=550 g/mol). The mixture was heated to 128° C., than 21 g ofLiOMe catalysts solution (10 wt % in methanol) were added slowly andn-butanol was slowly distilled off under reduced pressure. Catalystaddition was repeated 5 times each after one hour with 21 g catalystsolution. The transesterification was conducted in total for 6 h untilthe calculated amount of n-butanol had been distilled off.

918 g of polymer were obtained; Mn=13305, PDI=1.31

Anaylsis via GPC as well as 1H_NMR indicate almost quantitativeconversion of the MPEG-OH.

According to analysis via ¹H-NMR, the degree of polymerization is:P(nBA-MPEGA)=(58-19).

The 50 wt % solids solution in water displays an LCST of 70° C.

For testing as pigment dispersant part of the polymer A7 was dissolvedin water to give a clear 50 wt % solids solution.

Example A8 Synthesis of a Random Copolymer Poly(n-BA-MPEGA) ComprisingDifferent MPEG-OH: MPEG350. MPEG500. MPEG2000

In a 250 mL flask equipped with a magnetic stirring bar and distillationcolumn are loaded 65 g of a P(nBA) (Mn=8386, PD=1.21; made analog toexample A4), 7.5 g of MPEG-OH (M=350), 7.5 g MPEG-OH (M=500) and 20 gMPEG-OH (M=2000). The mixture was heated to 125° C. and 2 g of LiOMecatalyst solution (10 wt % in MeOH) were slowly added. Thetransesterification was started by slowly distilling off n-butanol underreduced pressure and increasing the temperature to 130° C. Twoadditional portions each of 2 g catalyst solution were added after 1 hand 2 h later. After 4 h total reaction time the transesterification wasterminated after the calculated amount of n-butanol had been distilledoff.

84 g of polymer were obtained; Mn=10490, PDI=1.61

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH-mixture.

According to analysis via ¹H-NMR, the degree of polymerization is:P(nBA-MPEGA-mix)=(69-7).

Example A9 Synthesis of a Random Copolymer Poly(n-BA-MPEGA) ComprisingDifferent MPEG-OH: MPEG350. MPEG500. MPEG5000

In a 250 mL flask equipped with a magnetic stirring bar and distillationcolumn are loaded 65 g of a P(nBA) (Mn=8386, PD=1.21; made analog toexample A4), 7.5 g of MPEG-OH (M=350), 7.5 g MPEG-OH (M=500) and 20 gMPEG-OH (M=5000). The mixture was heated to 125° C. and 2 g of LiOMecatalyst solution (10 wt % in MeOH) were slowly added. Thetransesterification was started by slowly distilling off n-butanol underreduced pressure and increasing the temperature to 130° C. Twoadditional portions each of 2 g catalyst solution were added after 1 hand 2 h later. After 4 h total reaction time the transesterification wasterminated after the calculated amount of n-butanol had been distilledoff.

83 g of polymer were obtained; Mn=9563, PDI=1.75

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH-mixture.

According to analysis via ¹H-NMR, the degree of polymerization is:P(nBA-MPEGA-mix)=(71-6).

Example A10 Synthesis of a Random Copolymer Poly(n-BA-MPEGA-OleA)Comprising Unsaturated Groups

In a 250 mL flask equipped with a magnetic stirring bar and distillationcolumn are loaded 38 g of a P(nBA) (Mn=8386, PD=1.21; made analog toexample A4), 35 g MPEG-OH (M=500) and 27 g oleyl alcohol (techn. grade).The mixture was heated to 125° C. and 2 g of LiOMe catalyst solution (10wt % in MeOH) were slowly added. The transesterification was started byslowly distilling off n-butanol under reduced pressure and increasingthe temperature to 135° C. Two additional portions each of 2 g catalystsolution were added after 1 h and 2 h later. After 4 h total reactiontime the transesterification was terminated after the calculated amountof n-butanol had been distilled off. 78 g of liquid polymer wereobtained; Mn=13374, PDI=1.87

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH and the unsaturated oleyl alcohol.

According to analysis via ¹H-NMR, the degree of polymerization is:P(nBA-MPEGA-OleA)=(32-18-26).

Example A11 Synthesis of a Non-Polar Block CopolymerPoly[(n-BA-iC12-15A)-b-4VP]

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 83.3 g of a 60 wt % MPA-solution of a diblockcopolymer P(nBA-b-4VP) (synthesized analog polymer A5; degree ofpolymerization=76-b-14, Mn=8834, PD=1.27) and 54.1 g of a branchediso-C12-15-alcohol mixture (Lial 125, Condea). After heating the mixtureto 125° C., the MPA was distilled under reduced pressure before adding0.28 g catalyst solution (Ti(AcAc)₂(iOPr)₂Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol). Thetransesterification was started by slowly distilling off n-Butanol underreduced pressure and increasing the temperature to 145° C. Twoadditional portions each of 0.28 g catalyst solution were added after 1h and 2 h later. After 4 h total reaction time the transesterificationwas terminated after no further n-butanol formation was observed.

76 g of liquid block copolymer were obtained; Mn=12216, PDI=1.27

Analysis via GPC as well as ¹H-NMR indicated almost quantitativeconversion of the MPEG-OH and the branched iC12-C15-alcohol.

According to combined analysis of ¹H-NMR and GPC, the degree ofpolymerization is: P[(nBA-iC12-15A)-b-4VP]=(16-60)-b-14.

Example A12 Synthesis of a Block Copolymer Poly(n-BA-b-S)

In a 500 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 210 g of a P(nBA) (synthesized analog polymer A4;degree of polymerization=76, Mn=8547, PDI=1.19) and 90 g of styrene andwere heated under N2 to 125° C. After 5 h the reaction was terminatedand the non-reacted styrene was distilled off at reduced pressure.

175 g of block copolymer were obtained; Mn=11828, PDI=1.21

According to analysis of ¹H-NMR the degree of polymerization is:P(nBA-b-S)=(75-b-40).

The resultant very high viscous block copolymer was diluted with MPA toa clear 60 wt % solution.

Example A13 Synthesis of a Non-Polar Block CopolymerPoly[(n-BA-iC12-15A)-b-S]

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 50 g of a 60 wt % MPA-solution of the diblockcopolymer A12 P(nBA-b-S)=75-b-40) and 26.3 g of a branchediso-C12-15-alcohol mixture (Lial 125, Condea). After heating the mixtureto 125° C., the MPA was distilled off under reduced pressure beforeadding 0.15 g catalyst solution (Ti(AcAc)₂(iOPr)₂Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol). Thetransesterification was started by slowly distilling off n-Butanol underreduced pressure and increasing the temperature to 145° C. Twoadditional portions each of 0.15 g catalyst solution were added after 2h and 4 h later. After 6 h total reaction time the reaction wasterminated after no further n-butanol formation was observed.

49 g of liquid block copolymer were obtained; Mn=15072, PDI=1.21

Analysis via GPC as well as ¹H-NMR indicated good conversion of thebranched iC12-C15-alcohol.

According to combined analysis of ¹H-NMR and GPC, the degree ofpolymerization is: P[(nBA-iC12-15A)-b-S=(15-60)-b-40.

Example A14 Synthesis of a Block Copolymer Poly(n-BA-b-DMAPMA)

In a 500 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 150 g of a P(nBA) (synthesized analog polymer A4;degree of polymerization=76, Mn=8547, PDI=1.19) and 150 g ofdimethylaminopropyl methacrylamide (DMAPMA) and were heated under N2 to145° C. After 4.5 h the reaction was terminated and non-reacted monomerDMAPMA was distilled off at high vacuum.

179 g of block copolymer were isolated; Mn=6874, PDI=1.41 (the apparentmolecular weight via GPC appeared lower than the starting precursor)

According to analysis of ¹H-NMR the degree of polymerization is:P(nBA-b-DMAPMA)=(75-b-23).

The resultant high viscous block copolymer was diluted with MPA to aclear 60 wt % solution.

Example A15 Synthesis of Block Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Transesterification Using MPEG-OH

50 g of the polymer Poly(n-BA-b-DMAPMA) (synthesized according topolymer A14) are loaded together with 50 g of MPEG-OH (M=550 g/mol) andsubjected to vacuum degassing at 130° C. for one hour to removenon-reacted DMAPMA. 2 g of LiOMe-solution (10 wt % lithium methanolatein methanol are added slowly and the transesterification started bydistilling off n-Butanol at 130° C. and reduced pressure. Catalystaddition is repeated 2 times each after one hour with 2 g catalystsolution. The transesterification is conducted in total for 3 h untilthe calculated amount of n-butanol had been distilled off.

100 g of polymer are obtained; Mn=112449, PDI=1.79

Anaylsis via GPC as well as 1H_NMR indicate almost quantitativeconversion of the MPEG-OH.

According to combined analysis of ¹H-NMR and GPC, the degree ofpolymerization is: P[(nBA-MPEG)-b-DMAPMA]=(51-14)-b-14.

Example A16 Synthesis of a Random Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Comprising Different MPEG-OH: MTG, MPEG500

In a 200 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 35 g of a Poly(n-BA-b-DMAPMA) (synthesized accordingto polymer A14), 15 g of MTG (M=164.2), 50 g MPEG-OH (M=500). Themixture is heated to 80° C. and 2 g of LiOMe catalyst solution (10 wt %in MeOH) are slowly added. The transesterification is started by slowlydistilling off n-butanol under reduced pressure and increasing thetemperature to 120° C. Two additional portions each of 2 g catalystsolution are added after 1 h and 2 h later. After 3 h total reactiontime the transesterification is terminated after the calculated amountof n-butanol had been distilled off.

100 g of polymer are obtained; Mn=11265, PDI=1.69

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH-mixture.

According to analysis via ¹H-NMR, the degree of polymerization is:P[(nBA-MPEG500A-MTGA)-b-DMAPMA]=(37-20-19)-b-14.

Example A17 Synthesis of a Random Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Comprising Different MPEG-OH: MTG, MPEG500

In a 200 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 40 g of a Poly(n-BA-b-DMAPMA) (synthesized accordingto polymer A14), 20 g of MTG (M=164.2), 40 g MPEG-OH (M=500). Themixture is heated to 80° C. and 2 g of LiOMe catalyst solution (10 wt %in MeOH) are slowly added. The transesterification is started by slowlydistilling off n-butanol under reduced pressure and increasing thetemperature to 120° C. Two additional portions each of 2 g catalystsolution are added after 1 h and 2 h later. After 3 h total reactiontime the transesterification is terminated after the calculated amountof n-butanol had been distilled off.

103 g of polymer are obtained; Mn=, PDI=

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH-mixture.

According to analysis via ¹H-NMR, the degree of polymerization is:P[(nBA-MPEG500A-MTGA)-b-DMAPMA]=(40-14-22)-b-14.

Example A18 Synthesis of a Random Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Comprising Different MPEG-OH: MTG, MPEG500

In a 200 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 40 g of a Poly(n-BA-b-DMAPMA) (synthesized accordingpolymer A14), 30 g of MTG (M=164.2), 30 g MPEG-OH (M=500). The mixtureis heated to 80° C. and 2 g of LiOMe catalyst solution (10 wt % in MeOH)are slowly added. The transesterification is started by slowlydistilling off n-butanol under reduced pressure and increasing thetemperature to 120° C. Two additional portions each of 2 g catalystsolution are added after 1 h and 2 h later. After 3 h total reactiontime the transesterification is terminated after the calculated amountof n-butanol had been distilled off.

100 g of polymer are obtained; Mn=, PDI=

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH-mixture.

According to analysis via ¹H-NMR, the degree of polymerization is:P[(nBA-MPEG500A-MTGA)-b-DMAPMA]=(33-11-33)-b-14.

Example A19 Synthesis of Block Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Transesterification Using MPEG-OH

In the reactor, 121.5 g of Poly(n-BA-b-DMAPMA) (synthesized according topolymer A14) are loaded together with 49.8 g of MPEG-OH (M=550 g/mol)and subjected to vacuum degassing at 130° C. for one hour to removenon-reacted DMAPMA. 0.33 g of LiOMe-solution (10 wt % lithiummethanolate in methanol are added slowly and the transesterificationstarted by distilling off n-Butanol at 130° C. and reduced pressure.Catalyst addition is repeated 3 times each after one hour with 0.33 gcatalyst solution. The transesterification is conducted in total for 6 huntil the calculated amount of n-butanol had been distilled off.

166 g of polymer are obtained; Mn=6972, PDI=2.12

Anaylsis via GPC as well as 1H_NMR indicate almost quantitativeconversion of the MPEG-OH.

According to combined analysis of ¹H-NMR and GPC, the degree ofpolymerization is: P[(nBA-MPEGA)-b-DMAPMA]=(62-15)-b-16.

Example A20 Synthesis of Block Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Transesterification Using MPEG-OH

In the reactor, 109.2 g of Poly(n-BA-b-DMAPMA) (synthesized according topolymer A14) are loaded together with 44.7 g of MPEG-OH (M=550 g/mol)and subjected to vacuum degassing at 130° C. for one hour to removenon-reacted DMAPMA. 1.19 g of catalyst solution (Ti(AcAc)2(iOPr)2Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) areadded slowly and the transesterification started by distilling offn-Butanol at 165° C. and reduced pressure. Catalyst addition is repeated2.5 times each after one hour with 1.19 g catalyst solution. Thetransesterification is conducted in total for 3.5 h until the calculatedamount of n-butanol had been distilled off.

149 g of polymer are obtained; Mn=8498, PDI=2.40.

Anaylsis via GPC as well as 1H_NMR indicate almost quantitativeconversion of the MPEG-OH.

According to combined analysis of ¹H-NMR and GPC, the degree ofpolymerization is: P[(nBA-MPEGA)-b-DMAPMA]=(65-12)-b-16.

Example A21 Synthesis of Block Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Transesterification Using MPEG-OH

In the reactor, 102.3 g of Poly(n-BA-b-DMAPMA) (synthesized according topolymer A14) are loaded together with 65.2 g of MPEG-OH (M=550 g/mol)and subjected to vacuum degassing at 160° C. for one hour to removenon-reacted DMAPMA. 0.43 g of catalyst solution (Ti(AcAc)2(iOPr)2Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) areadded slowly and the transesterification started by distilling offn-Butanol at 165° C. and reduced pressure. Catalyst addition is repeated4 times each after one hour with 0.43 g catalyst solution. Thetransesterification is conducted in total for 5 h until the calculatedamount of n-butanol had been distilled off.

163 g of polymer are obtained; Mn=8364, PDI=1.62

Anaylsis via GPC as well as 1H_NMR indicate almost quantitativeconversion of the MPEG-OH.

According to combined analysis of ¹H-NMR and GPC, the degree ofpolymerization is: P[(nBA-MPEG)-b-DMAPMA]=(60-17)-b-16.

Example A22 Synthesis of Block Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Transesterification Using MPEG-OH

In the reactor, 102.6 g of Poly(n-BA-b-DMAPMA) (synthesized according topolymer A14) are loaded together with 98.1 g of MPEG-OH (M=550 g/mol)and subjected to vacuum degassing at 160° C. for one hour to removenon-reacted DMAPMA. 0.52 g of catalyst solution (Ti(AcAc)2(iOPr)2Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) areadded slowly and the transesterification started by distilling offn-Butanol at 165° C. and reduced pressure. Catalyst addition is repeated4 times each after one hour with 0.52 g catalyst solution. Thetransesterification is conducted in total for 5 h until the calculatedamount of n-butanol had been distilled off.

196 g of polymer are obtained; Mn=9060, PDI=1.66

Anaylsis via GPC as well as 1H_NMR indicate almost quantitativeconversion of the MPEG-OH.

According to combined analysis of ¹H-NMR and GPC, the degree ofpolymerization is: P[(nBA-MPEG)-b-DMAPMA]=(51-26)-b-16.

Example A23 Synthesis of Block Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Transesterification Using MPEG-OH

In the reactor, 71.2 g of Poly(n-BA-b-DMAPMA) (synthesized according topolymer A14) are loaded together with 102.1 g of MPEG-OH (M=550 g/mol)and subjected to vacuum degassing at 160° C. for one hour to removenon-reacted DMAPMA. 0.6 g of catalyst solution (Ti(AcAc)2(iOPr)2Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) areadded slowly and the transesterification started by distilling offn-Butanol at 165° C. and reduced pressure. Catalyst addition is repeated4 times each after one hour with 0.6 g catalyst solution. Thetransesterification is conducted in total for 5 h until the calculatedamount of n-butanol had been distilled off.

170.2 g of polymer are obtained; Mn=10053, PDI=1.71

Anaylsis via GPC as well as 1H_NMR indicate almost quantitativeconversion of the MPEG-OH.

According to combined analysis of ¹H-NMR and GPC, the degree ofpolymerization is: P[(nBA-MPEG)-b-DMAPMA]=(39-38)-b-16.

Example A24 Synthesis of Block Copolymer Poly(n-BA-MPEGA-b-DMAPMA)Transesterification Using MPEG-OH

In the reactor, 54 g of Poly(n-BA-b-DMAPMA) (synthesized according topolymer A14) are loaded together with 120.5 g of MPEG-OH (M=550 g/mol)and subjected to vacuum degassing at 160° C. for one hour to removenon-reacted DMAPMA. 2.75 g of catalyst solution (Ti(AcAc)2(iOPr)2Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) areadded slowly and the transesterification started by distilling offn-Butanol at 165° C. and reduced pressure. Catalyst addition is repeated2 times each after 1 hour with 1.38 and 2.75 g catalyst solution. Thetransesterification is conducted in total for 6 h until the calculatedamount of n-butanol had been distilled off.

172 g of polymer are obtained; Mn=11051, PDI=1.72

Anaylsis via GPC as well as 1H_NMR indicate almost quantitativeconversion of the MPEG-OH.

According to combined analysis of ¹H-NMR and GPC, the degree ofpolymerization is: P[(nBA-MPEG)-b-DMAPMA]=(23-54)-b-16.

Example A25 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 75 g of a Poly(n-BA-b-DMAPMA) (synthesized accordingto polymer A14), 36.2 g MPEG-OH (M=500) and 12.1 g Lial 125 (techn.grade). The mixture is heated to 130° C. and 2.4 g of LiOMe catalystsolution (10 wt % in MeOH) are slowly added. The transesterification isstarted by slowly distilling off n-butanol under reduced pressure andincreasing the temperature to 125° C. Two additional portions each of2.4 g catalyst solution are added after 1 h and 1 h later. After 3 htotal reaction time the transesterification is terminated after thecalculated amount of n-butanol had been distilled off.

120.5 g of liquid polymer are obtained; Mn=8637, PDI=1.92

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH and Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-MPEGA-iC12-15A)-b-DMAPMA=(53-13-10)-14.

Example A26 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 70.1 g of a Poly(n-BA-b-DMAPMA) (synthesized accordingto polymer A14), 22.5 g MPEG-OH (M=500) and 22.5 g Lial 125 (techn.grade). The mixture is heated to 130° C. and 2.25 g of LiOMe catalystsolution (10 wt % in MeOH) are slowly added. The transesterification isstarted by slowly distilling off n-butanol under reduced pressure andincreasing the temperature to 125° C. Two additional portions each of2.25 g catalyst solution are added after 1 h and 1 h later. After 4 htotal reaction time the transesterification is terminated after thecalculated amount of n-butanol had been distilled off.

112.6 g of liquid polymer are obtained; Mn=8382, PDI=1.92

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH and Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-MPEGA-iC12-15A)-b-DMAPMA=(47-10-19)-14.

Example A27 Synthesis of a block copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 72 g of a Poly(n-BA-b-DMAPMA) (synthesized accordingto polymer A14), 11.6 g MPEG-OH (M=500) and 34.7 g Lial 125 (techn.grade). The mixture is heated to 130° C. and 2.31 g of LiOMe catalystsolution (10 wt % in MeOH) are slowly added. The transesterification isstarted by slowly distilling off n-butanol under reduced pressure andincreasing the temperature to 125° C. Two additional portions each of2.31 g catalyst solution are added after 1 h and 1 h later. After 4 htotal reaction time the transesterification is terminated after thecalculated amount of n-butanol had been distilled off.

115 g of liquid polymer are obtained; Mn=9488, PDI=1.77

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH and Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-MPEGA-iC12-15A)-b-DMAPMA=(54-2-20)-14.

Example A28 Synthesis of a Block Copolymer Poly(n-BA-iC12-15A)-b-DMAPMA) Transesterification Using Lial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 89.8 g of a Poly(n-BA-b-DMAPMA) (synthesized accordingto polymer A14), 57.7 g Lial 125 (techn. grade). The mixture is heatedto 130° C. and 2.9 g of LiOMe catalyst solution (10 wt % in MeOH) areslowly added. The transesterification is started by slowly distillingoff n-butanol under reduced pressure and increasing the temperature to125° C. Two additional portions each of 2.9 g catalyst solution areadded after 1 h and 1 h later. After 3 h total reaction time thetransesterification is terminated after the calculated amount ofn-butanol had been distilled off.

144 g of liquid polymer are obtained; Mn=10215, PDI=1.70

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-iC12-15A)-b-DMAPMA=(52-24)-14.

Example A29 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 535.5 g of a Poly(n-BA-b-DMAPMA) (synthesizedaccording to polymer A14), 84.8 g MPEG-OH (M=500) and 254.4 g Lial 125(techn. grade). The mixture is heated to 140° C. and 5.5 g of LiOMecatalyst solution (10 wt % in MeOH) are slowly added. Thetransesterification is started by slowly distilling off n-butanol underreduced pressure and increasing the temperature to 140° C. Twoadditional portions each of 5.5 g catalyst solution are added after 1 hand 1 h later. After 3 h total reaction time the transesterification isterminated after the calculated amount of n-butanol had been distilledoff.

751 g of liquid polymer are obtained; Mn=9488, PDI=1.77

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH and Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-MPEGA-iC12-15A)-b-DMAPMA=(52-4-23)-21.

Example A30 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 577.5 g of a Poly(n-BA-b-DMAPMA) (synthesizedaccording to polymer A14), 91.4 g MPEG-OH (M=500) and 274.3 g Lial 125(techn. grade). The mixture is heated to 140° C. and 7.4 g of catalystsolution (Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate,75 wt % in isopropanol) are added slowly and the transesterificationstarted by distilling off n-Butanol at 150° C. and reduced pressure. Twoadditional portions each of 7.4 g catalyst solution are added after 1 hand 1 h later. After 3 h total reaction time the transesterification isterminated after the calculated amount of n-butanol had been distilledoff.

826 g of liquid polymer are obtained; Mn=9488, PDI=1.77

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH and Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-MPEGA-iC12-15A)-b-DMAPMA=(52-4-23)-21.

Example A31 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 151.4 g of a Poly(n-BA-b-DMAPMA) (synthesizedaccording to polymer A14), 101.0 g MPEG-OH (M=500). The mixture isheated to 130° C. and 2.04 g of catalyst solution (Ti(AcAc)2(iOPr)2Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) areadded slowly and the transesterification started by distilling offn-Butanol at 155° C. and reduced pressure. Two additional portions eachof 2.04 g catalyst solution are added after 1 h and 1 h later. After 3 htotal reaction time the transesterification is terminated after thecalculated amount of n-butanol had been distilled off.

238.1 g of liquid polymer are obtained; Mn=7417, PDI=1.51

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-MPEGA-iC12-15A)-b-DMAPMA=(62-15)-17.

Example A32 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 150 g of a Poly(n-BA-b-DMAPMA) (synthesized accordingto polymer A14), 75 g MPEG-OH (M=500) and 25 g Lial 125 (techn. grade).The mixture is heated to 150° C. and 2.02 g of catalyst solution(Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % inisopropanol) are added slowly and the transesterification started bydistilling off n-Butanol at 155° C. and reduced pressure. Two additionalportions each of 2.02 g catalyst solution are added after 1 h and 1 hlater. After 3 h total reaction time the transesterification isterminated after the calculated amount of n-butanol had been distilledoff.

235.8 g of liquid polymer are obtained; Mn=7585, PDI=1.53

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH and Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-MPEGA-iC12-15A)-b-DMAPMA=(54-13-9)-17.

Example A33 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 150 g of a Poly(n-BA-b-DMAPMA) (synthesized accordingto polymer A14), 50 g MPEG-OH (M=500) and 50 g Lial 125 (techn. grade).The mixture is heated to 150° C. and 2.02 g of catalyst solution(Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % inisopropanol) are added slowly and the transesterification started bydistilling off n-Butanol at 155° C. and reduced pressure. Two additionalportions each of 2.02 g catalyst solution are added after 1 h and 1 hlater. After 3 h total reaction time the transesterification isterminated after the calculated amount of n-butanol had been distilledoff.

235.8 g of liquid polymer are obtained; Mn=7574, PDI=1.48

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH and Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-MPEGA-iC12-15A)-b-DMAPMA=(51-8-17)-17.

Example A34 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 153.7 g of a Poly(n-BA-b-DMAPMA) (synthesizedaccording to polymer A14), 25.6 g MPEG-OH (M=500) and 76.8 g Lial 125(techn. grade). The mixture is heated to 150° C. and 2.07 g of catalystsolution (Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate,75 wt % in isopropanol) are added slowly and the transesterificationstarted by distilling off n-Butanol at 155° C. and reduced pressure. Twoadditional portions each of 2.07 g catalyst solution are added after 1 hand 1 h later. After 3 h total reaction time the transesterification isterminated after the calculated amount of n-butanol had been distilledoff.

241.6 g of liquid polymer are obtained; Mn=7260, PDI=1.54

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of the MPEG-OH and Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-MPEGA-iC2-15A)-b-DMAPMA=(48-3-25)-17.

Example A35 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC2-15A)-b-DMAPMA) Transesterification Using MPEG-OH andLial 125

In a 250 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 152.7 g of a Poly(n-BA-b-DMAPMA) (synthesizedaccording to polymer A14), 101.8 g Lial 125 (techn. grade). The mixtureis heated to 130° C. and 2.06 g of catalyst solution (Ti(AcAc)2(iOPr)2Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) areadded slowly and the transesterification started by distilling offn-Butanol at 150° C. and reduced pressure. Two additional portions eachof 2.06 g catalyst solution are added after 1 h and 1 h later. After 3 htotal reaction time the transesterification is terminated after thecalculated amount of n-butanol had been distilled off.

240.1 g of liquid polymer are obtained; Mn=6766, PDI=1.58

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-iC12-15A)-b-DMAPMA=(46-30)-17.

Example A36 Synthesis of a Block Copolymer Poly(n-BA-MPEGA-iC12-15A)-b-DMAPMA) Transesterification using MPEG-OH andLial 125

In a 250 mL flask equipped with a magnetic stirring bar and distillationcolumn are loaded 152.7 g of a Poly(n-BA-b-DMAPMA) (synthesized analogpolymer A14), 101.8 g Lial 125 (techn. grade). The mixture is heated to130° C. and 2.06 g of catalyst solution (Ti(AcAc)2(iOPr)2Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) areadded slowly and the transesterification started by distilling offn-Butanol at 150° C. and reduced pressure. Two additional portions eachof 2.06 g catalyst solution are added after 1 h and 1 h later. After 3 htotal reaction time the transesterification is terminated after thecalculated amount of n-butanol had been distilled off.

240.1 g of liquid polymer are obtained; Mn=6766, PDI=1.58

Analysis via GPC as well as ¹H-NMR indicate almost quantitativeconversion of Lial 125.

According to analysis via ¹H-NMR, the degree of polymerization is:P(n-BA-iC12-15A)-b-DMAPMA=(46-30)-17.

Synthesis of a Block CopolymerPoly(n-BA-MPEGA-iC12-15A)-b-(DMAPMA-CIBnDMAPMA) Quaternization

In a 100 ml flask equipped with a magnetic stirring bar and distillationcolumn are loaded 15 g of a Poly (n-BA-MPEGA-iC12-15A)-b-DMAPMA), 0.9 go-Chlorobenzylchloride and 15 g of 1-methoxy-2-propanol. The mixture isheated to 95° C. for 4 h.

After the reaction, 30.9 g of liquid polymer are obtained; Mn=, PDI=

¹H-NMR indicates quantitative conversion for quaternization.

(n-BA-MPEGA-iC12-15A)-b-(DMAPMA-CIBnDMAPMA)=(52-4-23)-(15-6).

Preparation of Poly(benzylmethacrylate-co-methacrylic Acid)—Binder:

24 g of benzyl-methacrylate, 6 g of methacrylic acid and 0.525 g ofazobisisobutyronitrile (AIBN) are dissolved in 90 ml of propylene glycol1-monomethyl ether 2-acetate (PGMEA). The resulting reaction mixture isplaced in a preheated oil bath at 80° C. After stirring for 5 hours at80° C. under nitrogen, the resulting viscous solution is cooled to roomtemperature and used without further purification. The solid content isabout 25%.

Preparation of Dispersion Films for Color Filter:

The following substances are placed into a 37 ml screw bottle:

for PG36/PY150 system 2.0 g pigment 13.4 g propylene glycol 1-monomethylether 2-acetate 0.6 g dispersant (solid) 4.0 g binder (25 wt % in PGMEAas mentioned above) 50.0 g zircon beads for PB 15:6 system 1.0 g pigment9.8 g propylene glycol 1-monomethyl ether 2-acetate 0.36 g dispersant(solid) 4.0 g binder (25 wt % in PGMEA as mentioned above) 0.04 gSolsperse 5000 (Avecia Limited) 50.0 g zircon beads for PR254 system 1.0g pigment 8.6 g propylene glycol 1-monomethyl ether 2-acetate 0.2 gdispersant (solid) 3.2 g binder (25 wt % in PGMEA as mentioned above)50.0 g zircon beads

Standard CF grade pigments used for the examples:

C.I. Pigment Green 36: Lionol Green 6YK, TOYO INK MFG Co. Ltd.

C.I. Pigment Yellow 150: Yellow E4GN-GT, Bayer AG

C.I. Pigment Blue 15:6: Lionol Blue E, TOYO INK MFG Co. Ltd.

C.I. Pigment Red 254: IRGAPHOR RED BT-CF, Ciba Specialty Chemicals

Standard high molecular weight dispersants used for the examples:

Ciba EFKA 4300, 4330, 4047: Ciba Specialty Chemicals Disperbyk 2000,2001: Altana-BYK Chemie Ajisper PB821: Ajinomoto Fine Techno

The bottle is sealed with an inner cup and then applied to a paintconditioner for 3 hours to give the final dispersion. The dispersionthus obtained is cast onto a glass substrate by means of a spin coating,wherein a layer thickness is adjusted to give a film having a desiredcolor points (by standard C light, observation 2 degree) by controllingrotation speed, then dried at 60° C. for 1 hour.

Optical properties of the dispersion films thus obtained are measured byuse of a spectrophotometer (UV-2500PC, Shimadzu) and contrastmeasurement equipment (Model CT-1, Tsubosaka Electric Co., Ltd). Thecolor points (C.I.E. 1931 x, y chromaticity diagram) are calculatedusing standard C light.

Viscosity measurements are performed by using a Brookfield Rheometer(Model DV-III) with a cone/plate set-up at 25° C.

For the particle size measurement dynamic light scattering (DLS) is used(Mircotrac UPA, Microtrac Inc., Nikkiso). For the measurement samplesare diluted with PGMEA by factor of 100.

Developability of the dispersion films are tested by dipping to alkalinedeveloper (Semi Clean DL-A4, Yokohama Oil & Fats Industry Co.,LTD/water=1/9). Classify developability to 3 types. Dissolve, Dissolvethen Peel, Peel. Dissolve type is suitable for color filter application.

TABLE 1 Performance data for a pigment system PG36(50%)/PY150(50%)sample details initial viscosity [mPa s] 1 week viscosity [mPa s] colorproperty (y = 0.60) dispersant solids [%] 11.5 rpm 115 rpm 11.5 rpm 115rpm x Y contrast A27 50 17 12 25 19 0.304 58.6 4063 A14 50 41 23 51 290.305 58.5 3997

TABLE 2 Developerbility for a pigment system PG36(50%)/PY150(50%) sampledetails dispersant solids [%] developerbility A27 50 Dissolve only A1450 Dissolve then Peel

In these examples, A27 related to this invention is compared to A14.

A27 gives lower initial viscosity, lower 1 week viscosity and highercontrast than A14.

In addition, A27 has the most suitable developerbility for color filterapplication.

TABLE 3 Performance data for a pigment system PB15:6 sample detailsinitial viscosity [mPa s] 1 week viscosity [mPa s] color property (y =0.13) dispersant solids [%] 11.5 rpm 115 rpm 11.5 rpm 115 rpm x Ycontrast A36 50 17 10 2 8 0.135 17.0 4360 A14 50 22 15 18 14 0.135 17.04270 A14a 50 60 10 7 10 0.135 17.0 4300

A14a: the polymer of Example A14 (Poly(n-BA-b-DMAPMA)) is 30%quaternized with 4-chlorobenzylchloride.

TABLE 4 Developerbility for a pigment system PB15:6 sample detailsdispersant solids [%] developerbility A36 50 Dissolve only A14a 50Dissolve then Peel

In these examples, A36 related to this invention is compared to A14(Poly(n-BA-b-DMAPMA)) and to A14a which is the polymer of Example A14(Poly(n-BA-b-DMAPMA)) 30% quaternized with 4-chlorobenzylchloride.

A36 gives lower initial viscosity, lower 1 week viscosity and highercontrast than A14, A14a In addition, A36 has the most suitabledeveloperbility for color filter application.

TABLE 5 Performance data for a pigment system PG36(50%)/PY150(50%)sample details initial viscosity [mPa s] 1 week viscosity [mPa s] colorproperty (y = 0.60) dispersant solids [%] 11.5 rpm 115 rpm 11.5 rpm 115rpm x Y contrast A27 50 17 12 25 19 0.304 58.6 4063 Ajisper 100 15 14152 54 0.306 58.3 3570 PB821 Disperbyk 40 45 26 191 53 0.305 58.1 37832000 Disperbyk 46 36 23 301 62 0.308 58.5 3822 2001

TABLE 6 Developerbility for a pigment system PG36(50%)/PY150(50%) sampledetails dispersant solids [%] developerbility A27 50 Dissolve onlyAjisper PB821 100 Peel only Disperbyk 2000 40 no data Disperbyk 2001 46Peel only

In these examples, A27 related to this invention is compared todifferent commercial available dispersants which are used for colorfilter application.

A27 gives lower initial viscosity, lower 1 week viscosity and highercontrast than commercial available dispersants.

In addition, A27 has the most suitable developerbility for color filterapplication.

TABLE 7 Performance data for a pigment system PR 254 initial viscosityparticle size sample details [mPa · s] [μm] dispersant solids [%] 11.5rpm 115 rpm D50 D90 Ciba EFKA-4047 35 139 36 0.25 0.34 Ciba EFKA-4300 65126 36 0.24 0.46 Ciba EFKA-4330 65 100 34 0.24 0.35 Example A2 60 134 550.15 0.25 Comparative 60 104 44 0.15 0.24 Example A3

In this example A3 related to this invention is compared to differentcommercial available dispersants. Example A3 gives smaller particlesize, which is an indication for an improved dispersion containingprimary particles only. A complete de-agglomeration is achieved.

1. A method for producing a color filter, which comprises coating asubstrate with a color filter composition, followed by exposure toeffect photo-cure of the color filter composition, and development,wherein the color filter composition comprises a) a photoresist binder,b) a transparent pigment, c) optionally a solvent and/or optionally aphotoinitiator or a photolatent catalyst, d) a dispersant which is apolymer or copolymer obtained by a process comprising the steps of a1)polymerizing in a first step one or more ethylenically unsaturatedmonomers in the presence of at least one nitroxylether having thestructural element

wherein X represents a group having at least one carbon atom and is suchthat the free radical X• derived from X is capable of initiatingpolymerization; or a2) polymerizing in a first step one or moreethylenically unsaturated monomers in the presence of at least onestable free nitroxyl radical

 and a free radical initiator; wherein at least one monomer used in thesteps a1) or a2) is a C₁-C₆ alkyl or hydroxy C₁-C₆ alkyl ester ofacrylic or methacrylic acid; and a second step b) comprisingmodification of the polymer or copolymer prepared under a1) or a2) by atransesterification reaction, an amidation, hydrolysis or anhydridemodification or a combination thereof; and optionally in addition byquaternization.
 2. A method according to claim 1, wherein the dispersantis a polymer or copolymer obtained by a process comprising the steps ofa1) or a2) and a second step b) comprising the modification of thepolymer or copolymer prepared under a1) or a2) by a transesterificationreaction, an amidation, hydrolysis or anhydride modification or acombination thereof and in addition by quaternization.
 3. A methodaccording to claim 1 wherein the dispersant is obtained by a processwherein first polymerization step is carried out according to a1).
 4. Amethod according to claim 1 wherein the dispersant is obtained by aprocess wherein second step b) is a transesterification reaction.
 5. Amethod according to claim 1 wherein the structural element

is a structural element of formula (I)

wherein G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl or G₁ and G₂ or G₃and G₄, or G₁ and G₂ and G₃ and G₄ together form a C₅-C₁₂cycloalkylgroup; G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or agroup COOC₁-C₁₈alkyl; X is selected from the group consisting of—CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN,(CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl and (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl and * denotes a valence.
 6. Amethod according to claim 1 wherein the structural element

is a structural element of formula (II)

wherein G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl or G₁ and G₂ or G₃and G₄, or G₁ and G₂ and G₃ and G₄ together form a C₅-C₁₂cycloalkylgroup; G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or agroup COOC₁-C₁₈alkyl.
 7. A method according to claim 1 wherein thestructural element of formula (I) is a compound of formula (O1)


8. A method according to claim 1 wherein the monomer in step a1 or a2 isselected from isoprene, 1,3-butadiene, α-C₅-C₁₈alkene, 4-vinyl-pyridine,4-vinyl-pyridinium-ion, 2-vinyl-pyridine, 2-vinyl-pyridinium-ion,vinyl-imidazole, vinyl-imidazolinium-ion, dimethylacrylamide,3-dimethylaminopropylmethacrylamide, styrene, α-methyl styrene, p-methylstyrene, p-tert-butyl-styrene and a compound of formulaCH₂═C(R_(a))—(C═Z)-R_(b), wherein R_(a) is hydrogen or methyl, R_(b) isNH₂, O⁻(Me⁺), unsubstituted C₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted byat least one N and/or O atom, or hydroxy-substituted C₁-C₁₈alkoxy,unsubstituted C₁-C₁₈alkylamino, di(C₁-C₁₈alkyl)amino,hydroxy-substituted C₁-C₁₈alkylamino or hydroxy-substituteddi(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂An⁻; An⁻is a anion of a monovalent organic or inorganic acid; Me is a monovalentmetal atom or the ammonium ion and Z is oxygen or sulfur.
 9. A methodaccording to claim 1 wherein the dispersant is obtained by a processwherein in step b the alcohol is an unsubstituted linear or branchedC₈-C₃₆alkyl mono alcohol or mixtures thereof or a mono alcohol derivedfrom ethylenoxide, propylenoxide or mixtures thereof with up to 100 Catoms. 10-11. (canceled)
 12. A method according to claim 2 wherein thedispersant is obtained by a process wherein first polymerization step iscarried out according to a1).
 13. A method according to claim 2 whereinthe dispersant is obtained by a process wherein second step b) is atransesterification reaction.
 14. A color filter composition comprisinga) a photoresist binder, b) a transparent pigment, c) optionally asolvent and/or optionally a photoinitiator or a photolatent catalyst, d)a dispersant which is a polymer or copolymer obtained by a processcomprising the steps of a1) polymerizing in a first step one or moreethylenically unsaturated monomers in the presence of at least onenitroxylether having the structural element

 wherein X represents a group having at least one carbon atom and issuch that the free radical X• derived from X is capable of initiatingpolymerization; or a2) polymerizing in a first step one or moreethylenically unsaturated monomers in the presence of at least onestable free nitroxyl radical

 and a free radical initiator; wherein at least one monomer used in thesteps a1) or a2) is a C₁-C₆alkyl or hydroxy C₁-C₆alkyl ester of acrylicor methacrylic acid; and a second step b) comprising modification of thepolymer or copolymer prepared under a1) or a2) by a transesterificationreaction with an alcohol and optionally in addition by quaternization,wherein the alcohol of the transesterification is an unsubstitutedlinear or branched C₈-C₃₆alkyl mono alcohol or mixtures thereof or amono alcohol derived from ethylenoxide, propylenoxide or mixturesthereof with up to 100 C atoms.
 15. A color filter composition accordingto claim 14, wherein the dispersant is a polymer or copolymer obtainedby a process comprising the steps of a1) or a2) and a second step b)comprising the modification of the polymer or copolymer prepared undera1) or a2) by a transesterification reaction and in addition byquaternization.
 16. A color filter composition according to claim 14wherein the dispersant is obtained by a process wherein firstpolymerization step is carried out according to a1).
 17. A color filtercomposition according to claim 14 wherein the structural element

is a structural element of formula (I)

wherein G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl or G₁ and G₂ or G₃and G₄, or G₁ and G₂ and G₃ and G₄ together form a C₅-C₁₂cycloalkylgroup; G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or agroup COOC₁-C₁₈alkyl; X is selected from the group consisting of—CH₂-phenyl, CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN,(CH₃)₂CCN,

—CH₂CH═CH₂, CH₃CH—CH═CH₂ (C₁-C₄alkyl)CR₂₀—C(O)-phenyl,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl and (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl and * denotes a valence.
 18. Acolor filter composition according to claim 14 wherein the structuralelement

is a structural element of formula (II)

wherein G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl or G₁ and G₂ or G₃and G₄, or G₁ and G₂ and G₃ and G₄ together form a C₅-C₁₂cycloalkylgroup; G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or agroup COOC₁-C₁₈alkyl.
 19. A color filter composition according to claim14 wherein the structural element of formula (I) is a compound offormula (O1)


20. A color filter composition according to claim 14 wherein the monomerin step a1 or a2, is selected from isoprene, 1,3-butadiene,α-C₅-C₁₈alkene, 4-vinyl-pyridine, 4-vinyl-pyridinium-ion,2-vinyl-pyridine, 2-vinyl-pyridinium-ion, vinyl-imidazole,vinyl-imidazolinium-ion, dimethylacrylamide,3-dimethylaminopropylmethacrylamide, styrene, α-methyl styrene, p-methylstyrene, p-tert-butyl-styrene and a compound of formulaCH₂═C(R_(a))—(C═Z)-R_(b), wherein R_(a) is hydrogen or methyl, R_(b) isNH₂, O⁻(Me⁺), unsubstituted C₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted byat least one N and/or O atom, or hydroxy-substituted C₁-C₁₈alkoxy,unsubstituted C₁-C₁₈alkylamino, di(C₁-C₁₈alkyl)amino,hydroxy-substituted C₁-C₁₈alkylamino or hydroxy-substituteddi(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂An⁻; An⁻is a anion of a monovalent organic or inorganic acid; Me is a monovalentmetal atom or the ammonium ion and Z is oxygen or sulfur.